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Designation: D 1291 – 01
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D 1291 – 01
5.2 It is important to avoid over-chlorination in order to 7.5.3.2 Add 10 mL of acetic acid (1 + 1) (see 7.3) and 10
minimize chemical consumption, meet restrictions specified by mL of potassium iodide solution (see 7.8).
regulatory agencies, and minimize equipment degradation. 7.5.3.3 Titrate with sodium thiosulfate solution (0.10 N)
(see 7.11) until the yellow color of the liberated iodine is
6. Apparatus almost discharged.
6.1 All of the apparatus listed in Test Methods D 1293 and 7.5.3.4 Add 1 mL of starch indicator solution (see 7.12) and
D 1253 may be required. Any other apparatus necessary to continue the titration to a colorless endpoint.
carry out the final evaluation of the effects of chlorination will 7.5.3.5 Calculate the concentration of available chlorine as
be required. follows:
A 3 B3 35.45
7. Reagents and Materials Available chlorine, mg/mL 5 C
7.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
where:
all reagents shall conform to the specifications of the Commit-
A = sodium thiosulfate solution, standard, mL,
tee on Analytical Reagents of the American Chemical Society, B = normality of sodium thiosulfate solution, standard,
where such specifications are available. 3 Other grades may be and
used, provided it is first ascertained that the reagent is of C = chlorine solution titrated, mL.
sufficiently high purity to permit its use without lessening the 7.6 Hydrochloric Acid (1 + 1)—Mix equal volumes of con-
accuracy of the determination. centrated HCl (sp gr 1.19) and water.
7.2 Purity of Water—Unless otherwise indicated, references 7.7 Potassium Dichromate Solution (0.100 N)—Dissolve
to water shall be understood to mean reagent water conforming 4.904 g of anhydrous potassium dichromate (K2Cr2O7) of
to Specification D 1193, Type III, which has been rendered primary standard quality in water and dilute to 1000 mL in a
chlorine demand-free. Chlorine demand can be removed by volumetric flask.
treating with excess chlorine and allowing this treated solution 7.8 Potassium Iodide Solution (50 g/L)—Dissolve 50 g of
to stand in sunlight for several hours to destroy the chlorine potassium iodide (KI) in 1 L of freshly boiled and cooled water.
residuals. Test Method D 1253 may be used to assure complete Add 1 g of sodium bicarbonate (NaHCO3) to stabilize the
destruction of these residuals. solution. Store in an amber bottle and avoid direct exposure to
7.3 Acetic Acid Solution (1 + 1)—Mix equal volumes of sunlight.
glacial acetic acid and water. 7.9 Sodium Hydroxide Solution (10 g/L)—Dissolve 10 g of
7.4 Calcium Hydroxide Solution (10.7 g/L)—Weigh 10.7 g sodium hydroxide (NaOH) in water and dilute to 1 L.
of 100 % hydrated lime, Ca(OH)2, and suspend in water. Dilute
the suspension to 1 L. Shake well each time before using. NOTE 2—Caution: Heat is generated when dissolving sodium hydrox-
7.5 Chlorine Solution, Standard—Prepare one of the stan- ide in water.
dard solutions described in 7.5.1 and 7.5.2; standardize as 7.10 Sodium Thiosulfate Solution, Standard (0.10 N)—
described in 7.5.3. Transfer 25 g of sodium thiosulfate pentahydrate (Na2S2O3·
7.5.1 Chlorine Water—Pass chlorine gas through reagent 5H2O) to a 1-L volumetric flask containing about 800 mL
water until the solution contains from 0.5 to 10.0 mg/L Cl2. water. Dissolve the compound in the water by shaking and
NOTE 1—Warning: Use a slow rate of addition and carry out the periodic inversion. Add 1 g of sodium carbonate (Na2CO3) and
operation under a hood. Store in a glass stoppered amber bottle and dissolve. Dilute the solution to 1 L with water.
standardize daily before use. 7.10.1 Standardize the sodium thiosulfate solution: Add 70
7.5.2 Sodium Hypochlorite Solution, Standard—Dilute a mL of water to a porcelain dish, and add, with constant stirring,
commercial sodium hypochlorite or bleach solution containing 1 mL of concentrated sulfuric acid (H2SO4), 10.0 mL of 0.100
10 to 100 g of available chlorine per litre with water to provide N K2Cr2O7, and 20 mL of potassium iodide solution (see 7.8).
a solution containing from 0.5 to 10 mg available chlorine per Permit the reaction mixture to stand in the dark for about six
millilitre, depending upon the maximum expected chlorine minutes. Then titrate with the sodium thiosulfate solution until
requirement for the sample. This solution must be standardized the yellow color of the liberated iodine is almost discharged.
before use. Add 1 mL of starch indicator solution (see 7.12) and continue
7.5.3 Standardize the chlorine water or sodium hypochlorite the titration to a colorless endpoint.
solution, standard, as follows: 7.10.1.1 The normality can be calculated as:
7.5.3.1 Transfer 10 mL of the solution to be standardized to 1
Normality, Na2S2O3 5 Na S O required in titration, mL
a porcelain dish. 2 2 3
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D 1291 – 01
thoroughly and then add sufficient HCl (sp gr 1.19) to adjust 9.5 If the pH is higher than the desired pH range, carefully
the pH value of the solution to 4.0. Store in a glass-stoppered adjust the pH downward by adding, with constant gentle
bottle. Starch solution prepared in this manner will remain stirring, hydrochloric acid (1 + 1) dropwise until the pH
chemically stable for 1 year. reaches the upper limit of the desired range.
7.12 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
NOTE 6—Care must be taken during the addition of HCl (1 + 1) to make
(H2SO4). sure that the pH is not lowered too rapidly and that the lower limit of the
8. Sampling desired pH range is not exceeded. A rapid reaction (which itself lowers the
pH) may ensue if the pH is taken too low.
8.1 Collect the sample in accordance with Practices D 3370.
8.2 Conduct the test immediately following collection of the 9.6 Permit each portion of sample to stand for the desired
samples. contact time.
NOTE 7—Depending upon the application, a single contact time or a
9. Procedure series of different contact times may be used for each sample aliquot. This
NOTE 3—The area used for the test must not be in direct sunlight; tests is left to the judgment of the analyst.
should be run at the same temperature at which chlorination will be carried 9.7 To estimate chlorine requirement, perform whatever test
out. The temperature of the water just prior to, or immediately after,
is necessary on all of the sample aliquots at the end of the
chlorination must not exceed 50°C.
desired contact time to determine whether the objectives of
9.1 Transfer 500 mL portions of sample to separate 1000 chlorination have been met. If it is desired to maintain a certain
mL beakers. concentration of residual available chlorine, perform the chlo-
NOTE 4—The number of aliquots required to determine chlorine re- rine determination by Test Method D 1253.
quirement or demand is left to the judgment of the analyst. It will depend 9.8 To estimate chlorine demand, determine residual-free
upon the degree of familiarity that the analyst has with the water being chlorine on all of the sample aliquots at the end of the desired
tested as well as other variables. contact time by Test Method D 1253.
NOTE 5—One of two different sources of chlorine can be used in the
chlorine addition, either chlorine water or sodium hypochlorite solution.
In general, the type of chlorine that is used in the process should be used 10. Calculation
in the test. Chlorine water will tend to lower the pH of the water while 10.1 Calculate the chlorine dosage in milligrams per litre for
sodium hypochlorite solution will tend to raise the pH. each treated sample solution using Eq 1:
9.2 If chlorine water is used for chlorination, add the Chlorine dosage, mg/L 5 2AB
estimated maximum amount of chlorine (as chlorine water) to (1)
one of the sample aliquots. If sodium hypochlorite solution is
used for chlorination, add the estimated minimum amount of where:
chlorine (as sodium hypochlorite solution). Immediately mea- A = chlorinating solution added to each sample aliquot,
sure the pH of the sample aliquot by Test Method D 1293. If mL, and
the pH is not below the lower limit of the desired pH range, B = available chlorine per millilitre of chlorinating solu-
continue with 9.3. If the pH does fall below the lower limit of tion, mg (see 7.5.3).
the desired range, add sodium hydroxide solution dropwise 10.2 Chlorine demand is estimated using Eq 2:
with continual stirring to bring the pH up to approximately the Chlorine demand, mg/L 5 C 2 D
midpoint of the pH range, noting the amount of sodium (2)
hydroxide solution required. Then, discard this solution and where:
transfer another 500 mL aliquot of sample to a 1-L beaker to C = chlorine dosage, mg/L, and
replace it. Add the same amount of sodium hydroxide solution D = free chlorine remaining at the end of contact time,
as was required for pH adjustment of the first sample aliquot to mg/L.
all of the sample aliquots. Proceed to 9.3.
9.3 If the estimated maximum amount of chlorine was NOTE 8—To calculate chlorine consumed, see Appendix X1.
added to the first sample aliquot, add incrementally smaller 11. Precision and Bias
amounts of chlorine to each of the other sample aliquots, with
the estimated minimum amount of chlorine being added to the 11.1 Precision—The estimation of chlorine requirement or
last sample aliquot. If the estimated minimum amount of demand, or both, is a practice. For measuring chlorine values,
chlorine was added to the first sample aliquot, add incremen- this practice refers the user to Test Method D 1253. A statement
tally greater amounts of chlorine to each of the other sample for the precision and bias of chlorine measurement is located in
aliquots with the estimated maximum amount of chlorine being Test Method D 1253.
added to the last sample aliquot. Stir each sample aliquot
gently after addition of chlorine. Proceed to 9.4. 12. Keywords
9.4 Measure the pH of each sample aliquot by following 12.1 chlorine; disinfection; drinking water; residual chlo-
Test Method D 1293. rine; water treatment
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D 1291 – 01
APPENDIX
(Nonmandatory Information)
X1.1 Calculate the chlorine consumed for each sample X1.2.2 The straight lines for each chlorine dose are of the
aliquot at each contact time using Eq X1.1: general form described by Eq X1.2:
Chlorine consumed, mg/L 5 Chlorine dosage, mg/L D 5 Kt n
2 Chlorine residual, mg/L (X1.2)
(X1.1)
where:
X1.2 To determine the total amount of chlorine that would D = chlorine consumed, mg/L,
be consumed in a system over a period of time, plot the data as t = contact time, h,
follows: K = chlorine consumed after 1 h, mg/L, and
X1.2.1 On log-log graph paper, plot for a given sample n = slope of curve.
aliquot the chlorine consumed versus the contact time in hours. X1.2.3 The chlorine consumed can be interpolated between
Fit the best curve through the points. Determine the value of test values by use of the above expression.
the chlorine consumed at the intercept of the line with the X1.2.4 Where a number of chlorine doses are tested at a
coordinate corresponding to a contact time of 1 h. Designate given temperature and pH, the values of n may be averaged in
the value of this intercept as K. Determine the slope of the line order to develop a relationship between K and chlorine
and designate as n. application or between K and pH. If a family of such tests is
NOTE X1.1—Times in units other than hours may be appropriate for made at different temperatures, determine the relationship
certain applications. K should be determined at unit rate. The value for n between the logarithm of n and the reciprocal of the absolute
at a given temperature will vary with the characteristics of the water. temperature as a further aid to interpolation.
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